Method of making an agglomeration of fused microspheres

ABSTRACT

A method of making a fragrance delivery system comprising forming fused microspheres and incorparting a fragrance therein. The method relates to the mixing together of two separate factions comprising a silicate part and a modifier part, drying the mixture, heating the mixture to form an agglomeration, removing any free-flowing spheres from the agglomeration, soaking the agglomeration in fragrances or essential oils, and then drying the agglomeration.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a division of application Ser. No.09/302,270, filed on Apr. 30, 1999 now U.S. Pat. No. 6,245,733 andtitled “Arificial Rock Fragrance Delivery System,” by Jim Mosbaugh.application Ser. No. 09/302,270 has been allowed but has not yet issued.The present application claims the benefit of application Ser. No.09/302,270 and incorporates the contents by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for making fragrance deliverysystems. In particular, the invention relates to a method of makingpre-glass agglomerations that adsorb fragrance producing oils andvolatiles, and releases the fragrance innate to the oils and volatilesover an extended period of time without being messy or wet.

2. Description of the Related Art

Most delivery systems that utilize microspheres are manufactured out ofacrylates or nonsiliceous polymers. There are no fragrance deliverysystems that utilize soda lime borosilicate microspheres fused togethernaturally without additives. Most fragrance systems have a short lifespan and lose their aroma within a few months. Virtually no currentlyavailable fragrance systems last for longer than a few months under anycircumstances. Most also have a very intense smell initially with areasonably pleasant odor after a few weeks which fades fairly fast.

Microspheres have been used in the past for a variety of purposes. Themost common uses pertain to holders for chemicals in compositions suchas holding fragrance for laundry detergent In other words, themicrospheres contain a chemical and are mixed with other compounds toform a heterogeneous composition where the microspheres will release thechemicals either gradually or all at once in response to a stimulus suchas a change in ionic character, heat or other stimulus. Microspheres arealso used in drug delivery systems designed to release the drugcontained in the microsphere at a particular time according to pH orother factor.

The material and use of the pre-glass agglomeration created by thisinvention are unique and unknown in the past. Also, these pre-glassagglomerations are not discrete spheres but rather modified soda-limeborosilicate sphere clusters, wherein thousands of microspheres becomemolecularly fused together via microcrystalline like structures on thesphere surfaces. Therefore, this invention provides a method of making amicrosphere matrix without the addition of costly binders and polymers.These microcrystalline structures are distinctly different from currentavailable industrially manufactured microspheres.

U.S. Pat. No. 3,365,315 issued to Beck, et al. on Jan. 23, 1968,discloses glass bubbles made from glass cullet particles by heating.This amorphous solid contains SiO₂ (60-80%), Na₂O (5-26%), CaO (5-25%),K₂O/Li₂O (5-16%), and Na₂O/K₂O/Li₂O (5-16%) plus some other oxides. Thetemperature range utilized for bubble formation is between 1050° and1300° C. The resultant amorphous solid can be utilized as ingredients inmolded parts designed for use in high pressure environments. Theseparticles also have the capacity be used with thin walls thus possessinga maximum strength and crushable if that strength is exceeded. Themethods utilized to make the glass bubbles taught by Beck, as well asthe glass bubbles themselves, are very different from the rock of thepresent invention.

U.S. Pat. No. 3,985,298 issued to Nichols on Oct. 12,1976, discussescontrolled release materials, and method of using, that can beincorporated into a chemical delivery system. The materials utilized byNichols are polymer-liquid composite materials which may contain 99% ormore of the liquid. These controlled release materials can beincorporated into aerosol propellants, food products, chewing gum,pharmaceutical compounds, agricultural products, or cosmeticpreparations. The desired functions of the release materials areflavoring, scent, coloring, medication, is dermatological action,pesticidal action, or agricultural fertilizer. The materials andobjectives utilized by Nichols are different from the present invention.

U.S. Pat. No. 4,155,897 issued to Schlusener on May 22, 1979, disclosescompositions exhibiting controlled release of an active substance. Thecompositions of Schlusener comprise an unsaturated polyester resin, anactive substance, hollow microspheres of an organic material, and aninorganic material. The hollow microspheres can be made of glass and aremixed with an unsaturated polyester resin to make a molded solid orsemisolid substance. An active ingredient, such as volatile oils, isadded to the substance. The strength of the final product depends on theunsaturated polyesters used, but is less than the strength of theunsaturated polyester used because the hollow microspheres reduce theoverall strength. The composition taught by Schlusener, and the methodof making the composition, are different from the amorphous rock of thepresent invention, and the method of making it. The release of gas bythe molded item is measured by a period of up to about half a year whichis significantly less than the year and a half capacity of the presentinvention. There is a relatively high gas release rate the first week,less the next three weeks and even less for the remainder of the activetime. Also, the compositions of Schlusener lacks the strength and lowdensity combination of the present invention.

U.S. Pat. No. 5,336,665 issued to Garner-Gray, et al. On Aug. 9, 1994,discloses a hydrophobic porous inorganic carrier particle having aperfume absorbed into the particle. In particular, a detergentcomposition containing the carrier particle and a method formanufacturing the same is disclosed. The inorganic carriers used inGamer-Gray include aluminosilicates such as certain zeolites, clays,aluminas and silicas, all of which are chemically treated or naturallyhydrophobic. These porous, inorganic carrier particles are not designedto release odor over an extended period of time, but to deliver perfumeto clothing or other surface via a detergent or the like. The particlesused in Garner-Gray are not designed for room deodorizers, are notstrong, and are not exceptionally adsorbent in that they are hydrophobicand would not adsorb water or alcohols.

U.S. Pat. No. 5,725,869 issued to Lo on Mar. 10, 1998, describesmicrosphere reservoirs for controlled release applications. Themicrospheres, optionally containing an ingredient to be dispensedthrough controlled release, are prepared by solvent evaporation of anoil-in-water emulsion formed from an organic solvent containing apolymer and a plasticizer and an aqueous solution containing one or moreemulsifying agents. The microcapsules formed are porous and spongy instructure as opposed to hollow. These microspheres have a relativelyhigh load rate and a low dispersion rate. They are useful foragricultural chemicals, pharmaceuticals, cosmetics and fragrances. Theinvention of Lo is not designed to be a room deodorizer, and does nothave a sturdy solid nature as does the rock of the current invention.

U.S. Pat. No. 5,824,345 issued to Milstein on Oct. 20, 1998, disclosescompositions useful in the delivery of fragrances and flavorants. Amethod for preparing the compositions is disclosed: the active agent ismixed with the proteinoid of hydrolyzed vegetable protein solution andthe proteinoid or modified hydrolyzed vegetable protein is precipitatedout of the solution, thereby forming a microsphere containing the activeagent. The product formed by the method in Milstein differs from thepresent invention in that the present invention adsorbs any liquid, oilor alcohol, while Milstein requires the microspheres to be madeconcurrent with placing the agent therein which is a handicap in that itreduces the usefulness of the Milstein invention. Also, the microsphereof Milstein is not as sturdy as the current invention and the aroma doesnot last nearly as long.

U.S. Pat. No. 5,849,055 issued to Arai, et al. on Dec. 15, 1998,discloses a process for making inorganic microspheres which comprisespulverizing a material by wet pulverization to obtain a slurry of apulverized powder material, spraying the slurry to form liquid droplets,and heating the liquid droplets to fuse or sinter the powder material toobtain inorganic microspheres. These microspheres are discreteindividual microbeads and cannot be utilized in the manner of thepresent invention. The microspheres of Arai can be used as a powder oran ingredient, but not as a deodorizing rock.

U.S. Pat. No. 5,871,722 issued to Nacht, et al. on Feb. 16, 1999, showsionic beads usefully for controlled release and adsorption. Activeingredients are released from the ionic polymer beads over an extendedperiod of time such as when orally administered, or when applied to akeratinic material, typically human skin or hair, or when otherwisedelivered to a target environment. Clearly, the ionic beads of Nacht aredesigned to deliver an active ingredient upon contact with somesubstance which releases their ionic bonds. These ionic beads would notbe useful for room deodorants or absorption of oils.

U.S. Pat. No. 5,534,348 issued to Miller, et al. on Jul. 9, 1996,describes hollow borosilicate microspheres and a method of making them.The compositions of the sodium borosilicate starts with the preferredweight ratio of Na₂O:SiO₂:B₂O₃ between 1.0:2.5:0.2 and 1.0:3.22:0.5 forthe starting material. The borosilicate microspheres of Miller are usedin reflective paints and coatings, incorporated into molded plasticproducts, and f or use as thermal insulation, but not as deliveryvehicles for scents or as adsorbent materials.

None of the above inventions and patents, taken either singularly or incombination, is seen to describe the instant invention as claimed. Thus,a method of making an artificial rock fragrance delivery system solvingthe aforementioned problems is desired.

SUMMARY OF THE INVENTION

The current invention is a method for making a pre-glass agglomerationthat acts as a vector for fragrance delivery by utilizing fused,microspheres with calcium integrated into the spheres from an aqueoussol precursor. The artificial fragrance delivery system is also referredto herein as an artificial rock fragrance delivery system, because thepre-glass agglomeration resembles a rock or rock-like structure. Thefragrance delivery system has an extended fragrance release timegenerally exceeding a year and a half. The pre-glass agglomeration usesmicrocapillary action to quickly uptake oils and alcohols to more thandouble the weight of the pre-glass agglomeration. Also, the slow releaseof a fragrance without any residual liquid escape is anotheradvantageous quality of the instant pre-glass agglomeration invention.It is also possible to recharge or replenish the pre-glassagglomerations an unlimited number of times with additional fragranceoils/alcohols after the odor fades. The pre-glass agglomerations canalso be molded into a variety of shapes using conventional vacuumapplications to maintain the integrity of the resulting molded shape.

The pre-glass agglomerations with fragrance can be used for aromatherapycrock pots or boilers. They may also be dipped in flammable oils andused as incense or candle wicks. The pre-glass agglomerations can beused as room or facility fragrances, to counteract pungent odors, andmay be colored or dyed as desired.

The pre-glass agglomerations can also be used for various filtrationapplications. For example, they can be used for anionic and cationicseparation by modification of the metal groups in order to bind saltsfrom brine discharge in desalinization plants to economically reducesalt content. The pre-glass agglomerations can be used for separationfilters for chemical processes such as removal of chlorine or sulfatesfrom stacks. The surfaces, internal and external, of the pre-glassagglomerations can be modified by various acylations or substitutions toprovide functional groups which can aid in separations, chemicalcollections and catalysis. Additional separation methods include the useof the rocks in saline/petroleum separation with for example oil spills.

There are numerous other uses as well. They can be used as low weightbuoyancy control devices due to their extremely low density, andutilized as heat insulation and/or fire-resistant filler material. Also,they can be used as insect repellent by soaking the pre-glassagglomeration, having increased borate content, in citronella, lavenderor other repellant. Sodium bicarbonate can be adsorbed by these rocks toproduce fizzing in an essential oil bath. Naked or untreated pre-glassagglomerations can be used to adsorb various airborne chemical vapors,for example in nail salons and urethane production facilities.

Additionally, prior to high temperature processing, the powder may beapplied to various fabrics in order to achieve waterproofingcharacteristics. Thermal and sound insulation benefits also result. Itis notable that in order to achieve flexibility from the coated fabricit is necessary to incorporate various drying control chemicaladditives. The treated fabric is excellent for aeronautical applicationssuch as the insulation barrier between the fuselage and the exterior ofairplanes. Accordingly, it is a principal object of the invention toprovide a method of making an agglomeration of pre-glass material thathas exceptional absorption qualities, and is dry to the touch once driedand removed from the fluid to be adsorbed.

It is another object of the invention to provide a method of making anagglomeration of pre-glass material that can adsorb oils and otherlipophilic substances readily without significant mess. It is a furtherobject of the invention to provide a method of making an agglomerationof pre-glass material that can adsorb alcohol-based liquids readily.Still another object of the invention is to provide a method of makingan agglomeration of pre-glass material that after absorption of anaromatic oil/alcohol-based substance will release the fragrance of theadsorbed substance over an extended period of time. It is an object ofthe invention to provide a method of making improved elements andarrangements thereof for the purposes described which is inexpensive,dependable and fully effective in accomplishing its intended purposes.These and other objects of the present invention will become readilyapparent upon further review of the following specification.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention pertains to a highly adsorbent pre-glassagglomeration or rocks which can be utilized in diverse ways. Thepre-glass agglomeration can be used to adsorb oil/alcohol-based liquids.Upon absorption of liquids, the surface of the pre-glass agglomerationis dry to the touch, thus eliminating any potential mess or stickiness.The pre-glass agglomeration is a long term fragrance delivery systemthat will adsorb aromatic oil/alcohol based liquids, and then releasethe fragrance of the aromatic liquid slowly over a sustained period oftime, generally up to about one and a half years.

Colored liquid(s) and/or dye(s) can be used to decorate the pre-glassagglomeration, wherein the resulting pre-glass agglomeration has thecolor or dye of the liquid adsorbed therein. Also, the pre-glassagglomeration can be formed into various shapes as desired. Otherapplications include salt binding, filtration, separation andinsulation. As used herein, all percentages (%) are percent weight involume of water prior to heating, also expressed as weight/volume %,%(w/v), w/v, w/v % or simply %, unless otherwise indicated. Thefollowing example is the preferred embodiment of the pre-glassagglomeration according to the present invention. It should be noted,however, that the example is by no means a limitation of the invention,and that various modifications and improvements in the manufacturingprocess all fall under the scope of this invention.

EXAMPLE 1

SiO₂ from about 60 to about 75%;

Na₂O from about 10 to about 35%;

K₂O from about 2 to about 20%;

B₂O₃ from about 5 to about 20%; and

CaO from about 0.5 to about 12%

Preferably, commercial silicates are utilized such as sodium silicatehaving a weight ratio 3.22, or sodium silicate modified with a causticagent or acetate having a weight range between 2.8-3 silicate to alkali,or potassium silicates such as KASIL (PQ Corporation) having a weightratio 2.44 are used. Modifiers such as tech grade boric acid and calciumnitrate are also used. The slurry for the modifiers is approximately8-18% solids. The total solution is between 20-40% solids. Othermodifiers may be added in quantities from about 1-10% These othermodifiers may include Pb, MgO, Al₂O₃, BaO, Li₂O, Ge, and S.

A preferred method of making the pre-glass agglomeration of Example 1comprises the following steps: The constituents are mixed together intwo separate factions comprising the silicate part and the modifierpart. The modifier part is boric and calcium in an aqueous slurry. Themodifier solution is either poured into the silicate solution withvigorous mixing or the two are mixed together using an impeller pumpwith a recirculation loop. Vigorous mixing and slow addition of theboric/calcium solution are essential.

The solution, once mixed together, has a pH of 10-12. Mixingtemperatures approach 60° C. This solution is fed to a two fluid nozzlefor atomization via a diaphragm pump at 25-200 psi. Alternatively, acentrifugal atomizer may be utilized at 10,000-25,000 rpm. While airatomizing, air pressure varies between 80-1000 psi. The drying stepoccurs at about 100° C. to about 300° C. The outlet temperature is300-800° F.

The spray-dried product is then fed via pneumatic conveyor to a rotarytube furnace. The powder is fed into the furnace via an Accurate Feederto a 316 SS tube rotating at 7-12 rpm and an angle of reposeapproximately ⅛ to 5 inches per foot. The furnace has 4 discrete zoneswith a temperature profile from 200° C. to 1200° C. with either aco-current or a counter current dry air flow at approximately 25-200SCFH. Another atmosphere which is reducing, for example methane, may beused.

The pre-glass agglomeration is then collected from the furnace andsifted to remove any free flowing spheres from the pre-glassagglomeration. As a result of the sifting, the pre-glass agglomerationtakes on a smooth surface. Examination under 40× microscopy indicatedthousands of fused spheres.

The pre-glass agglomeration, once formed, is dipped into a solutioncontaining various fragrance(s) or essential oils and allowed to soakfor approximately 20-30 minutes. Conversely, the pre-glass agglomerationcan be placed in a shallow dish of oils and inserted into a highpressure oven at ambient temperatures to reduce absorption time. Theoils may also be dyed to impart color to the finished rock. Thepre-glass agglomeration is removed from the dip via a screening processand conveyed under a series of ultraviolet heat lamps in order to drythe pre-glass agglomeration to the touch.

Oils used in the absorption process are preferably cut with a carriersuch as dipropylene glycol, propylene glycol, SD alcohols, etc.Pre-glass agglomerations to be used in contact with the skin will useonly FDA approved carriers and oils.

Pre-glass agglomerations made by the above method can also be used toseparate oil from saline. Pre-glass agglomerations which have not beensoaked in a fragrance containing liquid are preferably used for this.

In order to separate oil from saline the pre-glass agglomerations areplaced in an oil and water dispersion and are mixed either by tidalaction or paddle. Allow the agglomerations to soak for up to 48 hoursand then collect the agglomerations with a screen or net. Place theagglomerations in either a conventional oven or a vacuum oven in orderto reclaim the petroleum. The reclaimed petroleum can then be recycled.The agglomerations can be discarded or reused. To reuse, theagglomerations must be washed with a low weight alcohol.

It is to be understood that the present invention is not limited to theembodiments described above, but encompasses any and all embodimentswithin the scope of the following claims.

I claim:
 1. A process for making an agglomeration of fused microspherescomprising the steps of: a. mixing silicates; b. mixing modifiers; c.mixing silicates and modifiers together to form a mixture; d. drying themixture to form a dry resultant material; e. heating the resultantmaterial to form an agglomeration; f. soaking the agglomeration in aliquid fragrance selected from the group consisting of an oil and analcohol; g. removing the agglomeration from the liquid fragrance; and h.drying the fragrance containing the agglomeration.
 2. A process formaking an agglomeration of fused microspheres as in claim 1, wherein:said silicates are sodium silicate and potassium silicate; and saidmodifiers are boric acid, Pb, MgO, Al₂O₃, BaO, Li₂O, Ge, S and calciumnitrate.
 3. A process for making an agglomeration of fused microspheresas in claim 1, wherein: a. the step of mixing the silicates and themodifiers together to form the mixture occurs by pouring the modifiersinto the silicates; b. the step of drying occurs with a spray dryer viaa diaphragm pump at 50-150 psi and atomizing at 80 to 300 psi withoutlet temperature ranging from about 300° to about 800° F.; and c. thestep of heating the resultant material occurs in a furnace by anaccurate feeder rotating 5-20 rpm at an angle of repose ⅛-5 inches perfoot at about 200° C. to about 1200° C. with a counter current dry airflow 25-200 SCFH.
 4. A process for making an agglomeration of fusedmicrospheres as in claim 2, wherein: a the step of mixing the silicatesand the modifiers together to form the mixture occurs by pouring themodifiers into the silicates; b. the step of drying occurs with a spraydryer via a diaphragm pump at 56-150 psi and atomizing at 80 to 300 psiwith outlet temperature ranging from about 300° to about 800° F.; and c.the step of heating the resultant material occurs in a furnace by anaccurate feeder rotating 5-20 rpm at an angle of repose ⅛-5 inches perfoot at about 200° C. to about 1200° C. with a co-current dry air flow25-200 SCFH.
 5. A process for making an agglomeration of fusedmicrospheres as in claim 2, wherein: a. the step of mixing the silicatesand the modifiers occurs by an impeller pump and a recirculation loop;b. the step of drying occurs with a spray dryer with a diaphragm pump at25-200 psi and air atomizing at 80 to 800 psi with an outlet temperatureranging from about 300° to about 800° F.; and c. the step of heating theresultant material occurs in a furnace by an accurate feeder rotating5-20 rpm at an angle of repose ⅛-5 inches per foot at about 200° C. toabout 1200° C. with a co-current dry air flow 25-200 SCFH.
 6. A processfor making an agglomeration of fused microspheres as in claim 2,wherein: a. the drying steps occurs at about 1000 to about 300° C.; andb. the step of heating the resultant material occurs in a furnace by anaccurate feeder rotating 5-20 rpm at an angle of repose ⅛-5 inches perfoot at about 200° C. to about 1200° C. with a co-current dry air flow25-200 SCFH.